Thioglycolic acid (TGA) is an organic compound widely used in cosmetics that cause a variety of health problems when overexposed to it. So far many attempts have been made to develop methods for TGA detection, but most of them need sophisticated instrumentations and are a little bit complicated. Therefore, a simple, cheap and sensitive detection method of TGA is highly desired. Herein, we demonstrated for the first time an Au−S bonding amplified, highly sensitive electrochemiluminescence (ECL) sensing method for TGA detection using tris(2,2′‐bipyridyl)ruthenium(II) (Ru(bpy)32+) as a luminophore and TGA as a self‐co‐reactant, via an anodic reaction at the Au electrode surface. Due to different molecular coordination environments of the TGA at the electrode surface, the ECL signal intensity of the developed ECL system gives much higher ECL signal in borate buffer than phosphate buffer of the same pH. Under the optimized experimental conditions, the ECL intensity has a direct relationship with the concentration of TGA in the range of 0.03 μM to 300 μM and a limit of detection of 0.013 μM (3σ/m). The reported ECL system has further been applied for the detection of TGA in cosmetics with acceptable recoveries.